阅读说明：本技术 一种引达省并二噻吩类光电化合物纯化方法 (Purification method of indacenodithiophene photoelectric compound ) 是由 王浩 张慧丽 肖淑勇 于 2020-12-31 设计创作，主要内容包括：本发明涉及一种引达省并二噻吩类光电化合物纯化方法,包括以下步骤：步骤1：将引达省并二噻吩类光电化合物溶解在溶剂1中,室温搅拌或热回流至完全溶解或溶解饱和,溶解饱和后过滤,将滤液继续回流；步骤2：向步骤1得到的溶液中滴入有溶剂2,观察到沉淀产生,继续搅拌；步骤3：将步骤2得到的悬浮液过滤,采用溶剂3洗涤滤饼,得到纯化后的IDT类化合物。本发明的提纯技术简单高效,易于操作且重复性好。具体提纯工艺涉及到常用的提纯技术,采用非常规的重结晶+热洗涤的方式达到了完全除去杂质的目的。通过此发明实现了此类有机中间体的高效提纯,大大提高了提纯效率,降低了此类有机光电材料的成本。(The invention relates to a purification method of indacenobithiophene photoelectric compounds, which comprises the following steps: step 1: dissolving the indacenodithiophene photoelectric compound in a solvent 1, stirring at room temperature or refluxing under heating until the indacenodithiophene photoelectric compound is completely dissolved or dissolved to saturation, filtering after the dissolution is saturated, and continuously refluxing the filtrate; step 2: dripping a solvent 2 into the solution obtained in the step 1, observing the generation of precipitates, and continuing stirring; and step 3: and (3) filtering the suspension obtained in the step (2), and washing a filter cake by using a solvent 3 to obtain the purified IDT compound. The purification technology of the invention is simple and efficient, is easy to operate and has good repeatability. The specific purification process relates to a common purification technology, and the purpose of completely removing impurities is achieved by adopting an unconventional recrystallization and hot washing mode. The method realizes the high-efficiency purification of the organic intermediate, greatly improves the purification efficiency and reduces the cost of the organic photoelectric material.)

1. A purification method of indacenodithiophene photoelectric compounds is characterized by comprising the following steps:

step 1: dissolving the indacenodithiophene photoelectric compound in a solvent 1, stirring at room temperature or refluxing under heating until the indacenodithiophene photoelectric compound is completely dissolved or dissolved to saturation, filtering after the dissolution is saturated, and continuously refluxing the filtrate;

step 2: dripping a solvent 2 into the solution obtained in the step 1, observing the generation of precipitates, and continuing stirring;

and step 3: and (3) filtering the suspension obtained in the step (2), and washing a filter cake by using a solvent 3 to obtain the purified IDT compound.

2. The method for purifying indacenodithiophene photoelectric compounds according to claim 1, wherein the indacenodithiophene compound has one of the following basic structures:

wherein, R1 is a straight chain or branched chain alkyl of 1-12 carbon atoms, R2 and R3 are one of hydrogen, aldehyde group, halogen group or 1.3 indene diketone compound group, and R2 and R3 are the same or different.

3. The method for purifying indacenodithiophene photoelectric compounds according to claim 1, wherein in the step one, the solvent 1 is one or a mixture of more of chloroform, dichloromethane, 1.2-dichloromethane and chlorobenzene, the thermal reflux temperature is the boiling point of the solvent 1, and the reflux time is 0.5-1 h.

4. The method for purifying indacenodithiophene photoelectric compounds according to claim 1, wherein in the second step, the solvent 2 is one or more of methanol, ethanol, hexane, and petroleum ether, the dropping amount of the solvent 2 is 1-20 times of the volume amount of the solvent 1, and the stirring time is 10-60min after the dropping.

5. The method for purifying indacenodithiophene photoelectric compounds according to claim 1, wherein in step three, the solvent 3 is one or more of methanol, ethanol, hexane, acetone, and petroleum ether, and the number of washing times is selected from 2 to 4.

Technical Field

The invention relates to the technical field of organic photoelectric material purification, in particular to a purification method of indacenobithiophene organic photoelectric materials.

Background

Solar cells have been developed in recent years as an important component of clean renewable energy. Among them, organic photovoltaic devices based on organic semiconductor materials have outstanding advantages of light weight, low cost, and capability of being made into flexible large-area devices, and have become one of the most active fields in photovoltaic research. By designing and synthesizing a wide variety of organic materials on the basis of molecules and optimizing the structure of a device, the organic material is expected to become one of important ways for future energy utilization, and has extremely wide market prospect. The focus of current research in the field of organic photovoltaics is the development of efficient donor and acceptor materials as photoactive layers. In recent years, organic conjugated small molecules have shown many advantages such as: the determined structure, molecular weight, high purity, batch stability and the like enable the research of the organic small-molecule solar cell to be rapidly developed.

The IDT-based organic small molecule is widely studied in polymer-fullerene solar cells, non-fullerene solar cells and the like in recent years, and the energy conversion efficiency of the non-fullerene solar cells prepared by using the IDT-based organic small molecule as an electron acceptor is far more than 10%. The Indacenodithiophene (IDT) unit has a planar linear structure, and the carbon skeleton of the unit is passed through SP³The hybridized carbon atoms are connected, so that the pi overlapped orbit can be maximized, stronger pi-pi accumulation is formed, and the energy disorder of molecular conformation is reduced. Meanwhile, the plane structure formed by the method is also beneficial to pi electron delocalization in molecules and accumulation and transmission of electrons, so that higher carrier mobility can be obtained to improve short-circuit current.

After the development of the IDT nucleus-based classical small molecule receptor material ITIC (Lin Y; Wang J; Zhang Z-G; Bai H; Li Y; Zhu D; Zhan X.Adv.Mater.,2015,27 (7): 1170-1174), the fused ring electron receptor, particularly the IDT receptor material, is just like the bamboo shoot after rain. The ITIC itself is also a star molecule for the A-D-A fused ring electron acceptor. In the design and synthesis of the A-D-A type photoelectric material, hybridized carbon atoms provide the positions of side chains in molecular design, and are connected with long alkyl chains through covalent bonds, so that the solubility of the material can be greatly improved, the influence caused by rigid groups is reduced, and the A-D-A type photoelectric material has good compatibility in later-stage solution processing and film formation by blending with donor materials. The design based on the IDT unit presents a plurality of high-efficiency small-molecule receptor materials, and the difficulty of synthesis and purification is brought by the corresponding complicated material design. Although many research groups can realize the synthesis and purification of the indacenodithiophene materials at present, the synthesis and purification difficulty is still very high according to the high price of the materials, and the synthesis and purification speed is a crucial factor for scientific research.

Based on the technical difficulties of synthesis and purification, the invention provides a simple and efficient separation and purification method of Indacenobithiophene (IDT) organic photoelectric materials. The method has universality in the Indacenodithiophene (IDT) materials, and is simple to operate and good in repeatability.

Disclosure of Invention

The invention aims to overcome the defects of the existing synthesis and purification technology and provides a simple and efficient purification method of a dithienothiophene (IDT) organic photoelectric material of the indacene.

A purification method of indacenodithiophene photoelectric compounds combines recrystallization and hot washing purification technologies to form a simple and easy-to-operate purification scheme. The specific implementation comprises the following steps:

step 1: dissolving the indacenodithiophene photoelectric compound in a solvent 1, stirring at room temperature or refluxing at a high temperature until the indacenodithiophene photoelectric compound is completely dissolved or is dissolved and saturated, filtering while the solution is hot after the dissolution and saturation, and continuously refluxing the filtrate for a certain time.

Step 2: and (3) dripping a solvent 2 with proper solubility into the solution obtained in the step (1), observing the generation of precipitates, and continuing stirring for a certain time.

And step 3: and (3) filtering the suspension obtained in the step (2), and washing a filter cake by using a solvent 3 to obtain the purified IDT compound.

The basic structure of the indacenodithiophene compound is one of the following structures:

wherein, R1 is a straight chain or branched chain alkyl of 1-12 carbon atoms, R2 and R3 are one of hydrogen, aldehyde group, halogen group or 1.3 indene diketone compound group, and R2 and R3 are the same or different.

Preferably, in the step 1, the solvent 1 may be selected from one or more of the following: dichloromethane, trichloromethane, 1, 2-dichloromethane, chlorobenzene, and the like. The thermal reflux temperature is the boiling point of the solvent 1 used, and the reflux time is selected to be 0.5-1 h.

Preferably, in the step 1, after the solution is saturated, the filtration mode is natural pressure filtration or glass sand funnel reduced pressure filtration. The temperature during the filtration process is controlled to be about the temperature when the solution is completely dissolved or saturated.

Preferably, in the step 2, the solvent 2 may be selected from one or more of the following: petroleum ether, acetone, methanol, ethanol, hexane, and the like. The amount of the solvent 2 to be dropped is selected to be 1 to 20 times the volume amount of the solvent 1. After the dripping is finished, the stirring time is selected to be 10-60 min.

Preferably, in the step 3, the washing solvent 3 may be selected from one or more of the following: petroleum ether, acetone, methanol, ethanol, hexane. The number of washing times is 2-4.

Preferably, in the step 3, the suspension is filtered by selecting a glass sand funnel reduced pressure filtration or a Buchner funnel reduced pressure filtration. The temperature during the filtration was chosen to be room temperature.

The invention has the advantages that: the indacenodithiophene photoelectric compound has simple purification process and high efficiency, and can obtain a target product with good quality only by simple modes of thermal dissolution, recrystallization, thermal washing and the like. The invention has mild purification conditions and high purity which can reach more than 98 percent, and is an ideal purification method.

Drawings

FIG. 1, the inventionOf the IDTT of the illustrative example 1¹HNMR atlas.

FIG. 2, map of 1HNMR of ITIC in example 2 of the present invention.

FIG. 3, TPTT-CHO in example 3 of the invention¹HNMR atlas.

Figure 4, map of IET 1HNMR in example 4 of the invention.

The specific implementation mode is as follows:

for the purpose of promoting an understanding of the invention, reference will now be made in detail to the embodiments of the invention illustrated in the accompanying drawings.

It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are only used for matching with the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions under which the present invention can be implemented, so that the present invention has no technical significance, and any structural modification, ratio relationship change, or size adjustment should still fall within the scope of the present invention without affecting the efficacy and the achievable purpose of the present invention.

The following examples are given to enable a person skilled in the art to understand the invention in its full scope, but do not limit it in any way:

example 1:

purification of IDTT of IDT-1 series compound: prior to this treatment, the product required a crude pass through the column.

Step 1: 30g of crude IDTT and 15ml of trichloromethane are added into a single-mouth glass bottle, and then the mixture is stirred and heated to reflux for 30min, and the IDTT is completely dissolved in the trichloromethane.

Step 2: 200ml of petroleum ether is measured and quickly dripped into the trichloromethane solution of IDTT through a dropping funnel, and heating and stirring are kept during the dripping process. After the dropwise addition, a large amount of yellow solid is separated out, and the heating is removed and the stirring is continued for 20 min.

And step 3: filter through buchner funnel under reduced pressure and rinse 3 times with petroleum ether. The yellow solid obtained was 27.6g after drying, 92% yield and 98.1% purity.

The structural formula of IDTT is shown as follows:

the corresponding nuclear magnetic diagram of the target product after IDTT purification is shown in figure 1. As can be seen from the nuclear magnetic spectrum, the figure has almost no miscellaneous peak, and the purity of the purified target product is very high.

Example 2:

purification of ITIC of IDT-1 series compound: prior to this treatment, the product required a crude pass through the column.

Step 1: 10g of crude ITIC and 500ml of dichloromethane were added to a glass one-neck flask, which was then stirred at room temperature for 1 h. Then filtering at room temperature under natural pressure to remove insoluble impurities.

Step 2: 750ml of acetone was measured and quickly added dropwise to the solution of ITIC in methylene chloride via a dropping funnel, with stirring being maintained during the dropwise addition. After the dropwise addition, a large amount of blue solid is separated out, and the stirring is continued for 30 min.

And step 3: filter through buchner funnel under reduced pressure and rinse 4 times with acetone. Finally, 9.6g of dark blue solid is obtained after drying, the yield is 96 percent, and the purity is 99.0 percent.

The structural formula of ITIC is shown below:

the corresponding nuclear magnetic diagram of the purified target product ITIC is shown in figure 2. As can be seen from the nuclear magnetic spectrum, the figure has almost no miscellaneous peak, and the purified target product ITIC has high purity.

Example 3:

purification of IDT-3 series compound TPTT-CHO: prior to this treatment, the product required a crude purification through a chromatographic column.

Step 1: 20g of crude TPTT-CHO and 20ml of dichloromethane were added to a glass single-neck flask and stirred at room temperature for 0.5 h. At this point the crude TPTT-CHO was completely dissolved in methylene chloride.

Step 2: 300ml of petroleum ether is measured and quickly dripped into a dichloromethane solution of TPTT-CHO through a dropping funnel, and stirring is kept during the dripping process. After the dropwise addition, a large amount of yellow solid is separated out, and the stirring is continued for 30 min.

And step 3: filter through buchner funnel under reduced pressure and rinse 2 times with acetone. The yellow solid obtained was 17.8g after drying, yield 89% and purity 98.3%.

TPTT-CHO has the following structural formula:

the corresponding nuclear magnetic map of the target product TPTT-CHO after purification is shown in figure 3. As can be seen from the nuclear magnetic spectrum, the figure has almost no miscellaneous peak, and the purity of the purified target product TPTT-CHO is very high.

Example 4:

purification of IDT-2 series of Compound IET: prior to this treatment, the product required a crude purification through a chromatographic column.

Step 1: 30g of crude IET and 30ml of dichloromethane are added to a single glass flask and then stirred to reflux for 30min, at which point the crude IET is completely dissolved in dichloromethane.

Step 2: 500ml of petroleum ether is measured and quickly dripped into a methylene chloride solution of IET through a dropping funnel, heating is removed in the dripping process, and stirring is kept. After the dropwise addition, a large amount of white solid is separated out, and the stirring is continued to room temperature.

And step 3: filter through buchner funnel under reduced pressure and rinse 3 times with petroleum ether. The final white solid obtained was 28.2g after drying, yield 94% and purity 99.2%.

The structural formula of IET is shown below:

the corresponding nuclear magnetic map of the target product IET after purification is shown in figure 4. As can be seen from the nuclear magnetic spectrum, the figure has almost no hetero-peak, and the purified target product IET has high purity.

The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and also comprise the technical scheme formed by equivalent replacement of the technical features. The present invention is not limited to the details given herein, but is within the ordinary knowledge of those skilled in the art.